Internal release agents for polyisocyanate addition polymerization, their use in the preparation of cellular, microcellular, and noncellular polyurethane-polyurea molded parts having improved demolding properties

Abstract

The invention relates to a process for the preparation of cellular, microcellular, and noncellular polyurethane polyurea molded parts with improved demolding characteristics through the reaction injection molding technique wherein unique internal mold release agents are used which are esters and/or amides prepared by reacting a mixture of montanic acid and a carboxylic acid having ten or more carbon atoms with a polyol, alkanolamine, or polyamine.

The embodiments of the invention in which an exclusive privilege or property is claimed are defined as follows: 
     
       1. In a process for the one-shot preparation of polyurethane polyurea polymers by reaction injection molding wherein polyisocyanates, polyols, aromatic diamines and chain extenders are reacted in the presence of catalysts and optional blowing agents, auxiliaries and additives, the improvement comprising reacting said components in the presence of an amount effective for mold release of an internal mold release agent comprising at least one compound selected from the group consisting of carboxylic acid esters, amides, and esteramides prepared by the reaction of a mixture of montanic acid and at least one aliphatic carboxylic acid having ten or more carbon atoms with at least one reactive hydrogen compound selected from the group consisting of polyols, alkanolamines, and polyamines, wherein said reactive hydrogen compounds have a functionality of at least two, and a molecular weight of from 60 to 400, and wherein said internal release agent posseses an amine number from 0 to 100. 
     
     
       2. The process of claim 1 wherein said mixture of montanic acid and at least one aliphatic carboxylic acid contains from 5 to 95 percent by weight of montanic acid. 
     
     
       3. The process of claim 1 wherein said mixture of montanic acid and at least one aliphatic carboxylic acid contains from 20 to 60 percent by weight of montanic acid. 
     
     
       4. The process of claim 1 wherein said aliphatic carboxylic acid is selected from the group consisting of stearic acid, palmitic acid, ricinoleic acid, linoleic acid, linolenic acid, behenic acid, tallow oil fatty acids, fish oil acids, lauric acid, tall oil acids, and oleic acid. 
     
     
       5. The process of claim 1 wherein said reactive hydrogen compounds contains one or more tertiary amino groups. 
     
     
       6. The process of claim 1 wherein said alkanolamine contains one or more tertiary amino groups. 
     
     
       7. The process of claim 1 wherein mixtures of (a) from 99.9 to 50 weight percent of at least one sterically hindered primary aromatic diamine whose amino groups are sterically hindered relative to polyisocyanates by at least one alkyl substituent on the ortho position of each amino group, and   (b) from 0.1 to 50 weight percent of at least one unsubstituted or substituted reaction primary aromatic diamine whose amino groups do not exhibit reduced activity relative to the polyisocyanates are used as the aromatic diamines, whereby the weight percents are based on the total weight of the mixture of (a) and (b).     
     
     
       8. The process of claim 6 wherein said aliphatic carboxylic acid is selected from the group consisting of oleic acid and tall oil acid. 
     
     
       9. The process of claim 8 wherein said alkanolamine is selected from the group consisting of triisopropanolamine and triethanolamine. 
     
     
       10. The process of claim 1 wherein said internal release agents are utilized in amounts of from 0.1 to 20 percent by weight relative to the sum of the weights of the polyisocyanate, polyol, aromatic diamine and chain extender. 
     
     
       11. The process of claim 1 wherein said internal release agent is prepared by the esterification of one mole of montanic acid; two moles of an aliphatic carboxylic acid selected from the group consisting of tall oil fatty acid, oleic acid, and their mixtures; with one mole of an alkanolamine selected from the group consisting of triethanolalmine, triisopropanolamine, or their mixtures. 
     
     
       12. The polymer produced by the process of claim 1. 
     
     
       13. The polymer produced by the process of claim 8. 
     
     
       14. An internal release agent comprising at least one compound selected from the group consisting of carboxylic acid esters, amides, and esteramides prepared by the reaction of a mixture of montanic acid and at least one aliphatic carboxylic acid having ten or more carbons, with at least one reactive hydrogen compound selected from the group consisting of polyols, alkanolamines, and polyamines, wherein said reactive hydrogen compounds have a functionality of at least two, and a molecular weight of from 60 to 400, wherein said internal release agent possesses an amine number of from 0 to 100, and wherein said mixture of montanic acid and at least one aliphatic carboxylic acid contains from 5 to 95 percent by weight montanic acid. 
     
     
       15. The composition of claim 14 wherein said aliphatic carboxylic acid is selected from the group consisting of stearic acid, palmitic acid, ricinoleic acid, linoleic acid, linolenic acid, behenic acid, tallow oil fatty acids, fish oil acids, lauric acid, tall oil acids, and oleic acid. 
     
     
       16. The composition of claim 14 wherein said reactive hydrogen compound contains one or more tertiary amino groups. 
     
     
       17. The composition of claim 16 wherein said alkanolamine is selected from the group consisting of triisopropanolamine and triethanolamine. 
     
     
       18. The composition of claim 14 wherein said mixture of montanic acid and at least one aliphatic carboxylic acid contains from 20 to 60 percent by weight of montanic acid. 
     
     
       19. In a process for the preparation of polyurethane, polyisocyanurate, and polycarbodiimide polymers by polyisocyanate addition polymerization wherein internal release agents are utilized, the improvement comprising performing said polymerization in the presence of an effective amount of the release agent of claim 14.